Nitrogenous condensation products

ABSTRACT

Nitrogenous condensation products and hydrolysis products thereof are provided wherein the condensate of a fatty acid and diamine is reacted with an unsaturated dicarboxylic acid or a partial ester thereof; optionally the product of such a reaction or a similar product obtained from an unsaturated monocarboxylic acid is further reacted with a halocarboxylic acid. The unhydrolyzed products can be formulated as imidazolines.

This is a division, of application Ser. No. 598,092 filed July 22, 1975,now U.S. Pat. No. 4,044,034.

FIELD OF THE INVENTION

This invention relates to condensation products of fatty acids anddiamines also known as imidazoline derivatives and hydrolysis productsthereof and particularly to the production thereof and to productshaving surfactant properties. The imidazoline derivatives are2-imidazolines but for convenience hereinafter the term imidazoline isused for materials.

BACKGROUND OF THE INVENTION

Various imidazoline derivatives particularly those having amphotericproperties have been suggested and used in surfactant compositions.Thus, in U.S. Pat. No. 3,408,361 of Hans S. Mannheimer dated Oct. 29,1968, certain hydroxyethyl imidazolines are described. Other art in U.S.patents is U.S. Pat. No. 2,155,877 to Waldmann (1939) and U.S. Pat. No.2,267,965 to Wilson (1941) and U.S. Pat. No. 2,520,102 to Tyron (1950).These imidazoline products are obtained by reacting a diamine forexample, one of the formula NH₂ C₂ NHR_(a) --OH and a fatty acid ofgeneric formula R--COOH wherein R is 5 to 25 carbon atoms and is alkylor alkenyl, R_(a) is R₁ (OR₁)_(n) in which R₁ is an alkylene of 2 to 4carbon atoms and n is 0 to 4. The amines used in preparing thecondensates have primary amino groups and a second primary or asecondary amino group in 1:2 position to each other. In the aforesaidUnited States Patent the diamine and fatty acid are reacted to removewater of reaction. When only one mole of water is removed an open-chainproduct is obtained, considered to be for example, in the instance wheren is 0 of the formula: ##STR1## which can be described as an amide. Ifmore than one mole of water is removed the imidazoline ring structure isconsidered to be formed giving for example, in the instance where n is 0product of formula: ##STR2## For convenience the imidazoline ringstructure in this specification is formalized: the correct formula is:##STR3## The imidazoline can be converted to the open-chain structure byhydrolysis and in the art these open-chain products whether originallyor by hydrolysis are regarded from many aspects as having the equivalentproperties to the imidazolines although not demonstrating the closedring structure. Moreover, the initial condensation product generallycontains a mixture of open-chain and ring closed (imidazoline) products.

The preparation of an imidazoline substituted in the 2-position by along chain aliphatic hydrocarbon radical is well described in theliterature and is readily carried out by reaction described abovebetween a carboxylic acid and a polyamine containing at least oneprimary amino group and at least one secondary amino group. Since toobtain the product of the present invention it is necessary to obtain atsome time the hydroxy group on a 1-aliphatic hydrocarbon substituentusually the hydroxy ethyl type amine is desirable but a hydroxy groupcan be substituted on to the appropriate 1-alkylene side-chain by thosemethods normal in the art.

A nitrogen on the ring has been further reacted with an alkylatingagent, for example, sodium chloroacetate, U.S. Pat. No. 2,528,378 ofMannheimer 1950) to provide structures considered as having the formula:##STR4## wherein R and R₁ are as defined above and R₃ is an alkylenegroup of 1 to 3 carbon atoms, for example, methylene.

When in hydrolyzed or open chain form such structures could be regardedas having the structure: ##STR5##

Correspondingly, the imidazolines may be reacted with a monocarboxylicunsaturated acid or ester (United Kingdom Pat. No. 1,078,101 of Arndt,1967 and U.S. Pat. No. 3,555,041 of Katz) to provide structuresconsidered as having the formula: ##STR6## wherein R and R₁ are asdefined above and R₂ is alkylene of 2 to 4 carbon atoms.

When in hydrolyzed or open chain form such structures could be regardedas having the structure: ##STR7##

As mentioned, in U.S. Pat. No. 2,528,378 there is described thepreparation of a condensate of a diamine with a fatty acid which is thenfurther reacted with a monohalo monocarboxylic acid particularly a metalsalt thereof.

Such products have been found to demonstrate various surfactant ordetergent properties and to be useful in products requiring good foamingproperties and particularly those requiring fine bubble structure withgood stability, for example, shampoo compositions. Nevertheless, despitethe improvements obtained there is still a need for improvement in foamstructure and stability of compositions particularly shampoocompositions. The present invention has as its objects imidazolines andthe related open-chain structures which products can also be describedas modified condensation products of diamines and fatty acids, havingimproved properties for use in detergent or surfactant compositions, forexample, shampoos.

SUMMARY OF THE INVENTION

The present invention provides certain nitrogenous compounds of theformula:

    R--A--R.sub.1 --O(R.sub.1 --O).sub.n --Ac

wherein R is alkyl or alkenyl aliphatic group of 5 to 25 carbon atoms;

each R₁ is alkylene of 2 to 4 carbon atoms and may be the same ordifferent;

n is 0 to 4;

A is selected from the group consisting of: ##STR8##

R₃ COOM is the residue of monocarboxylic acid of 2 to 5 carbon atoms--C_(x) H_(2x) --COOM wherein x is 1 to 4;

m is from 0 to 2;

y is 0 or 1;

M is H or a cation, for example, an alkali metal such as sodium orpotassium or an organic base;

Ac is selected from the group consisting of a residue of anα,β-unsaturated dicarboxylic acid of 4 to 5 carbon atoms, a partialester thereof, a salt of said acid or partial esters and --R₂ COOM;

--R₂ COOM is the residue of an α,β-unsaturated monocarboxylic acidwherein R₂ is alkylene of 2 to 4 carbon atoms, providing that if Ac is--R₂ COOM then m is greater than 0.

Preferably if Ac is the residue of a monocarboxylic acid --R₂ COOM theny+m is greater then 1.

Generally in these products a preferred fatty acid used in preparing thecondensate is lauric acid giving R as undecyl.

Preferably the compounds are of the formula: ##STR9## wherein R is alkylof 5 to 25 carbons and Ac is a residue of unsaturated dicarboxylic acidof 4 to 5 carbons, and particularly preferred as Ac are ##STR10##wherein R₄ is alkyl of 1 to 6 carbons.

A preferred hydrolyzed form is of formula: ##STR11##

Another preferred product is: ##STR12## wherein R is alkyl of 5 to 25carbons, m is from 1 to 2 and Acis a residue of an unsaturated mono- ordicarboxylic acid or half ester thereof and particularly one in which Ris undecyl, p is 1 or 2, m is from 1 to 1.3, and Ac is ##STR13## or--CH₂ CH₂ --COO.sup.θ, wherein Z is selected from the group consistingof M, H and R₄ which is alkyl of 1 to 6 carbons preferably 1 to 4, and Mis a cation.

From another aspect the invention comprises a modified condensationproduct of a diamine which is of formula NH₂ CH₂ CH₂ NHR_(a) --OHwherein R_(a) is as hereinbefore defined and preferably is R₁ which isalkylene of 2 to 4 carbon atoms with a fatty acid of formula R--COOHwherein R is as hereinbefore defined which reaction product has from 1to 2 mols of water removed during condensation. Said condensationproduct of the invention is the basic condensation product which ismodified by condensation with an unsaturated dicarboxylic acid or apartial ester thereof. The resulting product can be further modified byalkylation to add the residue of an alkanoic acid. Instead of adicarboxylic acid the basic condensation product can also be modified bycondensation with a monocarboxylic unsaturated acid, but such a reactionproduct must be further alkylated to add the residue of an alkanoicacid.

These compounds can be prepared from a condensation imidazoline productas previously described in this specification.

DETAILED DESCRIPTION OF THE INVENTION

Condensates and the preparation thereof are described in detail in theart for example in U.S. Pat. No. 3,408,361 to Mannheimer, although thepreparation of the starting materials of this invention is not confinedto such method and any technically appropriate method for thepreparation of such starting materials can be employed. Essentially, onemethod for the preparation of the starting materials is to condense adiamine and a fatty acid. The fatty acids can be replaced by esters,amides, anhydrides or halides. When one mole of water is removed duringsuch condensation the basic product will then be considered to be ofFormula I. More usually, more than one mole of water is removed and theproduct will then be considered to contain an appropriate amount ofimidazoline ring structure of Formula II. Hereinafter the termcondensate is applied to the immeidate product of such condensation offatty acid and amine with up to 2 mols of water being removed. Asalready indicated a hydroxy amine can be employed or the hydroxy groupcan be substituted in the hydrocarbon side chain at the 1-position afterformation of the condensation product by techniques customary in theart. The preferred method, however, is the use of a hydroxy alkylalkylene polyamine for reaction with the fatty acid.

The nature of the fatty acid residue is preferably a residue of a fattyacid of 6 to 26 carbon atoms, preferably 8 to 22 carbon atoms. Typicalacids are coconut, lauric oleic, tall oil fatty acids, stearic, sebacic,n-valeric, isovaleric, caproic, heptoic, caprylic, pelargonic, capric,undecylic, tridecylic, myristic, pentadyclic, palmitic, margaric,octadecyclic, nonadecyclic, linoleic, erucic acid, cyclohexyl acetic andarachidic. Naphthenic and long chain fatty acids having an aromatichydrocarbon radical connected directly to the aliphatic chain may beemployed while certain unsaturated analogues may be used, as can besubstituted analogues, including fluorinated analogues. The presence ofminor or even major amounts of impurity such as the unsaturated fattyacids for instance, is not necessarily detrimental and these can be usedas the primary fatty acid. The fatty acids can also include thoseobtained from the oils of fats of animal, marine or vegetable originincluding coconut, palm kernel and palm oil acids which contain fattyacids having at least 11 carbon atoms, also from soy bean, linseed,olive, rape seed, cotton seed, peanut and castor oil which contain largeproportions of unsaturated hydroxy fatty acids. Mixtures of fatty acidscan be employed. An ester can sometimes be employed, the alcohol beingsplit off during the reaction and being removed as by distillation.

While the invention is primarily described in relation to R₁ as ethyleneas already indicated other alkylene groups of 1 to 6 carbon atoms can beemployed for example, propylene, particularly isopropylene, isobutylene,n-butylene or secondary butylene and pentylene or hexylene groupsdepending on the choice of amine. A preferred amine isaminoethylethanolamine which gives R₁ as --CH₂ --CH₂ -- and anotherpreferred amine is aminoethylisopropanolamine. The alkylene amideadducts obtained by reacting a product wherein R_(a) is R₁ --OH with upto 4 mols of an alkylene oxide e.g., ethylene oxide or propylene oxidecan be employed as the initial amine for condensation with the fattyacid. Polyoxyalkylene amines prepared by other techniques can also beemployed.

The present invention is exemplified by a limited number of condensates.However, in view of the extensive art on said condensates which arerecognized as having equivalent properties it will readily be recognizedby those skilled in the art that any given fatty acid or diamine asexemplified can be replaced and results obtained which are within thenormal range of properties useable in the present invention.

The condensate whether regarded as pure imidazoline or as a mixture ofimidazoline and open-chain product or simply as a condensate is thenreacted to provide the products of the invention. The basic condensateis hereinafter referred to as the condensate.

Generally, the condensate is a mass which although solid at roomtemperatures can be melted without decomposition often at temperaturesbelow 100° C. The initial reaction product of the invention withunsaturated carboxylic acid can be obtained simply by adding carboxylicacid to molten condensate. Preferably, addition takes place over aperiod sufficient to allow even reaction without unnecessaryconcentration of the acid at any given time. The exact rate of additionof the acid to the molten condensate is simply a matter of technicalexpertise. The reaction conditions for the reaction between unsaturatedacid and condensation product can vary widely providing that theconditions are sufficiently vigorous to initiate the reaction betweenthe reactants. A temperature range of approximately 20° C. to 100° C. isavailable, although at too high a temperature one may have degradationof some products. The unsaturated acid or ester should be added at suchrate that the molar concentration in the reacting process at any giventime is such as to minimize polymerization and particularly selfpolymerization. The reaction can be carried out in solvents or simply byaddition of the unsaturated acid to the molten mass of condensationproduct. In that the reaction can be regarded essentially as a reactionof a hydroxy group with an unsaturated carboxylic acid, those techniquesavailable generally for such reactions can be employed, having regard tothe physical properties of the reactants.

The unsaturated dicarboxylic acids must have two carboxylic groups onadjacent carbon atoms and either between these two carbons orimmediately adjacent to them an unsaturated grouping. The preferredacids are those of 4 to 5 carbon atoms as exemplified by maleic,fumaric, itaconic.

The unsaturated dicarboxylic acid residues which can be employed in thefinal product include the partial esters thereof up to the half ester. Apartial ester can preferably be employed having from 25 to 50%esterification. By 25% esterification is meant that in a given amount ofacid up to 25% of the acid groups present are esterified and 50%esterification would mean that the half ester was formed. A preferredester is the half-ester or "50%" partial ester. While preferably in mostinstances the partial ester would be reacted with the condensate analternative route would be to react the free acid and then esterifypartially up to 50% the carboxylic groups in the product. Variousconventional esterification techniques for use in this reaction arereadily available to those skilled in the art. An alternative techniqueis to react a full ester and then hydrolyze either to a partial ester(50% or below) or completely to free acid.

The partial esters of the dicarboxylic acids include methyl esters,ethyl esters and other lower alkyl esters of up to 6 carbons, e.g.,hexyl ester.

When the resulting product is prepared substantially from unhydrolyzedmaterial it can be transformed into a hydrolyzed product by forming anaqueous solution and hydrolyzing preferably in the presence of a basefor instance sodium hydroxide, potassium carbonate, ammonia,monoethylamine, diethylamine, triethylamine and mono- di- or tri-ethanolamine.

The preferred base is sodium hydroxide. After hydrolysis it is generallydesirable to neutralize the base when used by addition of an acid,particularly an inorganic strong acid such as hydrochloric acid.However, even without hydrolysis the reaction product of condensate anda dicarboxylic acid or an ester thereof is a commerically significantproduct. In neutralizing, various acids can be employed includinghydrochloric acid, sulfuric acid, nitric acid, although hydrochloricacid is preferred. In the final product M, if not hydrogen, can be oneof the cations used customarily in the art of surfactant amphoterics butis customarily an alkali metal, for example, sodium or potassium, butorganic bases can also be employed.

In this hydrolysis as indeed in all the hydrolysis reactions describedherein fission of the imidazoline structure is most probably between the2-Carbon and 1-Nitrogen but can also be speculated as being at leastpartially between the 2-Carbon and 3-Nitrogen.

In many circumstances a final commercial product is obtained by additionof water to form a solution. The pH of such solutions will generally befrom 4 to 10 but is usually slightly acid particularly for unhydrolyzedmaterials to minimize spontaneous hydrolysis.

The condensation product can be reacted with a compound which generatesa residue of an unsaturated monocarboxylic acid of 3 to 5 carbons forexample acrylic acid or methyl acrylate. The reaction can be effected bysimple addition of, for instance, the acrylate at a temperature of from30° to 100° C. Thus, the acrylate can be added over a period of say oneto three hours followed by heating for from to 24 hours at from 50° to110° C. The final process can be under vacuum to remove any unreactedacrylate. The product can then be treated with water and caustic soda tohydrolyze and neutralize the acid groups. Acrylate monomers which aresuitable for reaction may be acrylic acid, methacrylic acid, methylacrylate, ethyl acrylate, methyl methacrylate, isopropyl, acrylate,acrylamide and/or acrylonitrile. The reaction is found to go tosubstantial completion under specific conditions and no particularcatalyst is required since it appears that the basicity of the tertiarynitrogen atoms is sufficient to self-catalyze the acrylic monomer adductreaction. Adduct formation can be obtained in some instances by simpleaddition of monomer acrylate to condensate at temperatures near roomtemperature although usually it is desirable to increase the temperatureto 60° C.-100° C. with removal of unreacted monomer under vacuum. Whenother than free acids are employed (e.g., acrylamide or acrylonitrile) aspecific hydrolysis step will be required to produce the free acid. Forexample boiling in aqueous system in the presence of a base at 90°-100°C. until ammonia is completely removed (or alcohol for esters).

There can be an additional alkylating reaction e.g. with a haloalkanoicacid, for instance sodium chloracetate. Preferably this reaction iseffected with hydrolyzed products. Since this reaction involesalkylation and possible quaternization of one of the nitrogen atoms thereaction is primarily available with open-chain compounds, i.e.,hydrolysates rather than the imidazolines. When the original reaction ofcondensate with the unsaturated carboxylate acid is with amonocarboxylic acid then this additional step is a necessary feature ofthe inventin. The alkylation can be carried out in a single stage inwhich both hydrolysis and reaction with a haloalkanoic acid issimultaneous or there can be an hydrolysis of the product followed bythe reaction with an alkylating agent such as an haloalkanoic acid.

A reaction with three mols of alkylating agent is visualised as shown inthe Formulae substituting onto the 1-position but substitution at the3-position may be possible with consequent effect on the structure ofthe hydrolyzed products. However even if a 3-position substitution iseffecfted hydrolysis may result in isomerising to form the samehydrolysis products as the 1-substitution.

A reaction with haloalkanoic acid can be carried out under a variety ofconditions either in the presence of a solvent or more usually in thepresence of an aqueous system. For instance the sodium haloacetate canbe added to the hydrolyzed system with heating and with or without theaddition of a base.

Thus, the condensate reaction product with the unsaturated carboxylicacid can be reacted with a monohalocarboxylic acid in the presence ofcaustic soda (sodium hydroxide in aqueous solution). In a preferred formone mol of the reaction mass is added to an aqueous solution containingone mol of the monohalo carboxylic acid and from 2.2 to 2.5 mols ofcaustic soda and the mix is then heated to a temperature ofapproximately 95° C. until there is no change in pH. The pH normallydrops from about 13 to approximately 8. Additional caustic soda is addedto increase the sum of caustic soda to approximately 3 mols and the massis maintained until there is a sparkling clear solution when adjusted toa pH of from 9 to 10.

Another reaction is as described in U.S. Pat. No. 2,407,645 to Bersworth(1946) wherein the hydrolyzed condensate reaction product withunsaturated acid is reacted with an alkali metal cyanide and aformaldehyde-yielding substance then hydrolysed to drive off ammonia.Such a reaction can be used to add 2 mols of alkanoic acid and then onecould react with haloalkanoic acid to add a further carboxyalkyl group.

Typical haloalkanoic acids are the sodium or potassium salts ofchloracetic acid, and α- or β-chloropropionic acids.

For reaction products with dicarboxylic acids up to three mols ofalkanoic acid residue can be substituted preferably 0-2. For reactionproducts of monoacarboxylic acids there must be some alkylation andagain up to three mols can be added but a preferred range is 1-2 mols.

In another method of reacting one can react the basic condensate withthe unsaturated acid then simply add water and alkali metalhaloalkanoate. Thereafter add alkali (e.g., sodium hydroxide) and heatto 100° C. for say one hour.

The final products are generally obtained in the form of aqueoussolution and may contain residues of reactants employed in preparing thefinal product. The adduct of unsaturated acid and condensation productcan be a commercial product as such without addition of water. As iscustomary in this art the pure product is often not recovered from theaqueous solution and determination of the structure of the product is aneducated estimate based on the chemistry involved and the properties ofthe solution or adduct.

These products have amphoteric properties wherein the unreactedcondensates are cationic in nature, therefore a test for completion ofreaction is the extent to which the final product forms clear aqueoussolutions at high and low pH values.

The products of the invention, particularly when in aqueous solution,are of value in various surfactant compositions and particularly inemulsions, cosmetics, detergents and can be combined with othersurfactants. Solutions of the products of the invention can comprise anaqueous solution with as major organic components, the product of theinvention. The organic content of such a solution can measure from 20 to90% by weight thereof for example 30 to 70%. The solutions representfinished products of commerce although they are frequently latercombined by customers with other materials to provide compositions fordifferent purposes especially in the field of cosmetic compositions.

The products of the invention are particularly valuable in shampoos inassisting in the rendering of conditioning agents particularly forinstance, polycationic cellulose derivatives, compatable with othersurfactants for instance sulfates. Moreover, certain of the products ofthe invention at the same time can assist an improving the skin and hairconditioning properties of cosmetic products. The products of theinvention are generally water-soluble as already indicated but some havethe advantage of limited solubility in dilute solutions.

The products of the invention as already mentioned can be incorporatedin cosmetic preparations where it is desired to emulsify an aqueousplace and the normally lipophilic phase such as mineral oil, which maybe the continuous one. The compounds and their organic sulfate complexesare generally non-antagonistic toward most cosmetic ingredients.

Certain of these products can form complexes which may be complex saltswith organic sulfates e.g. sodium lauryl sulphate, sodiumpolyoxyethylene (3.5) lauryl sulfates, sodium polyoxyethylene (3)tridecyl sulfate.

The compounds are useful as hair and skin conditioners, hair rinses,creams, fabric softeners, laundry applications and cationic emulsifiersand can be generally highly efficient hair and skin conditionersgenerally without markedly reducing foaming as do conventionalconditioners when used in solutions. The ratio of compound employed ofwater can be from 1.00 to 99.9% of the organic compound. The compoundscan also be used in textiles to improve textile finishing.

One of the most active areas in shampoo research is creating aconditioning property into the shampoo. It would be desirable if thenecessity of a post-shampoo cream rinse could be eliminated. A mosteffective, and widely used conditioning agent is a polycationiccellulose derivative, for example, one made by reacting cellulosederivatives with epichlorhydrin, then condensing with trimethylamine(commercially available as "Polymer JR" which is a Trademark of UnionCarbide Corp). One of the problems in using this type of resin (usuallyat a level of about one percent of the shampoo formula) is that it isincompatible with many compounds used in shampoos which are anionic.

The products of this invention tend to couple and compatibilize suchresins and organic sulfates. It is a valuable aspect of the productsemploying the residues of dicarboxylicacids and particularly partialesters of such unsaturated dicarboxylic acids that they act as couplingagents in shampoos containing such resins and organic sulfates. Theshampoos have all the desirable properties if this general type ofproduct, foaming and conditioning very well.

Adducts of esters of maleic acid, hydrolyzed and unhydrolyzed, coupleorganic sulfates and Polymer JR, to form clear or nearly clearsolutions, whereas adducts prepared from maleic acid and itaconic acidform homogeneous but cloudy or pearlescent mixtures.

Adducts prepared from esters of maleic acid also seem to foam betterthan the other products, when combined into shampoo formulationscontaining both organic sulfates and Polymer JR Resin.

Generally products which are not alkylated may have superiorconditioning properties to alkylated products but the latter aresuperior in foaming and lathering.

The invention will now be illustrated by examples:

EXAMPLE I Preparation of Condensate

Lauric acid aminoethylethanolamine condensate is prepared as describedin Example 1 of U.S. Pat. No. 3,408,361 by chargingaminoethylethanolamine to a vessel containing lauric acid heated atabout 100° C. and a mole ratio of said fatty acid to diamine of from 1to 1.096.

This product may be considered as consisting substantially of a productbelieved to be of the formula: ##STR14## Having regard to the particularmethod used for making this product it was considered to have primarilythe aforesaid structure but it will be appreciated that certain smallproportions of amide be present and different methods of preparationsmight give greater amounts of amide of the structure: ##STR15##

The approximate molecular weight of the condensate starting material ofthe present invention is 268.

PREPARATION OF REACTION PRODUCT OF INVENTION Lauric Condensate plusItaconic Acid

A glass flask equipped with stirrer and thermometer was charged with1185 g. (approx. 4.4 moles) molten condensate. Over a period of twohours, 664 g. (approx. 5.1 moles) itaconic acid was slowly added to themass, starting at 55° C. and ending at 71° C. Temperature was mantainedat 69° to 72° C., for 19 hours when 1849 g. of water was added. Theresulting thin, clear, amber colored product, cooled to room temperaturehad a pH of 4.3.

A 40% aqueous solution of this material, neutralized to pH 4.3 to 7 with50% NaOH solution, vigorously massaged onto the scalp and hair aftershampooing, foamed copiously, left the hair, after rinsing, relativelystatic- and snarl-free, with a smooth, soft feel.

The active content of this product is believed generally to conform tothe formula: ##STR16##

EXAMPLE II Lauric Condensate plus Itaconic Acid, Hydrolyzed

A glass flask equipped with stirrer, thermometer and reflux condenserwas charged with 1849 g. (approx. 4.4 moles) of the product of Example Ijust prior to addition of water. With stirring, the mass was heated to70° C. and 1849 g. of water and 500 g. of 50% aqueous NaOH solution wereadded, lowering the temperature to 62° C. It was heated to 70° C. Fiftypercent aqueous sodium hydroxide solution was added to the stirred massat 70° to 72° C., over a 3 hour period, keeping the pH, measured at 30°C., at 9.0 to 9.4. A total of 668 g. of 50% aqueous sodium hydroxidesolution was used. The mass was cooled and 265 g. of 31.5% hydrochloricacid solution was used to neutralize the product to pH 7.8. The finalproduct was clear and viscous.

A 40% aqueous solution of this material, neutralized to pH 4 to 7 withhydrochloric acid, vigorously massaged onto the scalp and hair aftershampooing, foamed copiously, left the hair, after rinsing, relativelystatic- and snarl-free, with a smooth, soft feel.

The active content of this product is believed to conform to thefollowing formula or one of its isomers: ##STR17##

EXAMPLE III Lauric Condensate plus Maleic Acid

A glass flask equipped with stirrer and was charged with 474 g. (approx.1.77 moles) molten condensate of Example I. Over a period of two hours,238 g. (2.04 moles) maleic acid was slowly added to the mass, startingat 65° C. and ending at 73° C. The mass was maintained at 66° to 74° C.,for 191/2 hours, when 711 g. of water was added. The resulting thin,clear, amber colored product, cooled to room temperature, had a pH of2.98.

A 40% aqueous solution of this material, neutralized to pH 4 to 7 with50% NaOH solution, vigorously massaged onto the scalp and hair aftershampooing, foamed copiously, left the hair, after rinsing, relativelystatic- and snarl-free, with a smooth, soft feel.

The active content of this product is believed to conform to theformula: ##STR18##

EXAMPLE IV Lauric Condensate plus Maleic Acid, Hydrolyzed

Example III was repeated using 1232 g. (approx. 4.6 moles) condensate ofExample I, 616 g. (5.31 moles) maleic acid and 1849 g. of water. Theheating period was 16 hours at 72° to 85° C. After the water had beenadded, 555 g. of 50% sodium hydroxide solution was added. The mass washeated six hours at 68° to 72° C., as an additional 100 g. of 50% sodiumhydroxide solution was slowly added to maintain the pH at 9.0 to 9.2.

1535 g. of this final reaction was neutralized to pH 7.58 with 81.0 g.31.5% HCl solution.

A 40% aqueous solution of this material, neutralized to pH 4 to 7 with50% NaOH solution, vigorously massaged onto the scalp and hair aftershampooing, foamed copiously, left the hair, after rinsing, relativelystatic and anarl-free, with a smooth, soft feel.

The active content of this product is thought generally to conform tothe following formula or one of its isomers: ##STR19##

EXAMPLE V Lauric Condensate plus Maleic Acid plus SodiumMonochloroacetate

A glass flask equipped with stirrer, thermometer and condenser wascharged with 2772 g. (approx. 2.93 moles) of the reaction product ofExample IV prior to having been neutralized with HCl. To this was added512 g. (approx. 4.39 mole) sodium monochloroacetate over a 20 minuteperiod between 50° and 53° C. The mass was heated to 97° C., over aperiod of 11/2 hours, while 512 g. water slowly was added and 50% sodiumhydroxide solution was added to maintain the pH of the reaction mass at8.6 to 9.4 (measured at 30° C.). Stirring with heating at 97° to 100°C., was continued for an additionnal 21/4 hours, maintaining the pH (30°C.) at 8.7 to 9.4. In all a total of 400 g. of 50% sodium hydroxidesolution was used. With cooling, an additional 1000 g. water was addedto yield a thin, clear, light amber colored product having a pH of 9.42,non-volatile content of 41.1% and a sodium cloride content of 5.02%.

A 40% aqueous solution of this material, neutralized to pH 4 to 7 withHCl gave a good head of foam when used as a hair shampoo, leaving thehair soft and manageable. It was practically non-irritating to the eyesof rabbits as tested according to the method of Draize.

The active content of this product is believed generally to conform tothe following formula or one of its isomers: ##STR20##

EXAMPLE VI Lauric Condensate plus Acrylic Acid plus SodiumMonochloroacetate

A glass flask equipped with stirrer, thermometer and reflux condenserwas charged with 1400 g. (5.22 moles) condensate of Example I. Withstirring, 434 g. (6.03 moles) acrylic acid was added over a 4 hr. 10min. period at between 65° and 70° C. The mass was stirred andmaintained at 57° to 77° C., for 211/2 hours, after which 1834 g. waterwas added.

To 680 g. (approx. 0.97 moles) of this reaction material was added 174.8g. (1.5 moles) sodium monochloroacetate over a 20 minute period, from50° to 60° C. The mass was heated to 98° C., over a period of 13/4hours, while 50° sodium hydroxide solution was added to maintain the pHof the reaction mass at 9.0 to 9.6 (measured at 30° C.). Stirring withheating at 98° C., was continued for an additional 31/4 hours,maintaining the pH (30° C.) at 9.0 to 9.3. In all a total of 194 g. of50% sodium hydroxide solution was used. With cooling, 175 g. water wasadded to yield a thin, clear, light amber colored product having a pH of9.36, nonvolatile content of 49.4% and a sodium chloride content of7.22%.

A 40% aqueous solution of this material, neutralized to pH 4 to 7 withHCl gave a good head of foam when used as a hair shampoo, leaving thehair soft and manageable. It was practically non-iritating to the eyesof rabbits as tested according to the method of Draize.

The active content of this product is thought generally to conform tothe following formula or one of its isomers: ##STR21##

EXAMPLE VII

A condensate is prepared according to Preparation I from each of thefollowing acids:

Run 1 Caproic acid

2 Capric acid

3 Myristic acid

4 Behenic acid

5 Oleic acid

6 Linoleic acid

7 Palmitic acid

Each of the condensation products is individually reacted with

(1) Maleic acid

(2) Itaconic acid

(3) Fumeric acid

(4) The half ethyl ester of maleic acid.

Runs 1, 3, and 7 are repeated aminoethylisopropanolamineamonoethylisopropanolamine and each of the products is reactedseparately with maleic acid.

The method employed is that of Example I in each case.

In each case a product is obtained which is soluble in water and hasgood foaming properties.

EXAMPLE VIII

Each of the condensation products of Runs 1 to 7 is reacted with maleicacid and hydrolyzed following the procedure of Example IV. Asatisfactory product is obtained in each case in terms of foamingproperties.

EXAMPLE IX

Each of the products from the reaction with maleic acid is hydrolyzed asin Example V and reacted with sodium chloroacetate using the conditionsof Example V. The product is satisfactory in each case in terms offoaming properties.

EXAMPLE X

Amino ethyl ethanolamine (NH₂ C₂ NHC₂ H₄ OH) is reacted as described inU.S. Pat. No. 2,528,378 to Mannheimer with lauric acid (Example I,references are the Examples of U.S. Pat. No. 2,528,378 which are herebyincorporated by reference), capric acid (Example 3), linseed fatty acid(Example 4), caproic acid (Example 5), stearic acid (Example 6), dodecylbenzoic acid (Example 7), myristic acid (Example 8). Thereafter eachconsdensate obtained is reacted with each of the following unsaturatedcarboxylic acids: maleic acid, fumaric acid and with monoethyl maleatefollowing the procedure of present Example I.

Each of the products when formed into solution as in Example I havesatisfactory foaming properties. The condensates with lauric acid andcaproic acid are reacted with acrylic acid as in Example VI and theresulting product is then reacted with in one instance sodiumchloracetate and in the second instance with sodium bromopropionatefollowing the procedure of Example VI to obtain an aqueous solution. Theresulting solutions have satisfactory foaming properties.

EXAMPLE XI Lauric Condensate plus Ethyl Maleate

A glass flask equipped with stirrer and thermometer was charged with 938g. (aporox. 3.5 moles) molten condensate Over a period of about twohours, 616 g. (approx. 4 moles) of a 94% ethanol solution ofmonoethylmaleate was slowly added to the mass, starting at 60° C. andending at 73° C. The temperature was maintained at 70° C. to 75° C., forabout 22 hours. 1554 g. water was added, to yield a clear, light amberliquid having a pH of 4.1 and a solids content of 46.7%.

EXAMPLE XII Lauric Condensate plus Ethyl Maleate, Hydrolyzed

2138 g. of the product of Example X was heated, with stirring, with 122.g 50% NaOH, to 90° C., the boiling point of the solution. A total of 300ml. distillate was collected and replaced with water as the temperatureslowly rose to 100° C. Fifty percent NaOH was added during this time tokeep the pH above 9.0. A total of 339 g. of 50% NaOH was used in all.When the boiling point of 100° C was reached, indicating essentially allthe ester was hydrolyzed and the ethanol removed, and the reactionproduct was cooled, 300 ml. of water was added back to the reactionmass. The resulting clear, amber solution has a pH of 10.0 and a solidscontent of 44.3%.

EXAMPLE XIII Lauric Condensate plus Maleic Acid Alkylated

To 10 mols of the product of Example III is added 4 mols of causticsoda, eight mols of sodium cyanide are added and 7.5 mols offormaldehyde are added. The conditions and methods of addition are asdescribed in Example I of U.S. Pat. No. 2,407,645. Addition of sodiumcyanide and formaldehyde is repeated after evolution of ammonia ceasesfor each batch addition. The resulting product in aqueous solution hasexcellent foaming properties.

EXAMPLE XIV

A number of examples of shampoos were prepared. Some typicalformulations follow.

    ______________________________________                                        A.  Condensate of lauric acid and                                                 aminoethylethanolamine reacted                                                with monoethylmaleate, hydrolyzed.                                                                  22.6     10.0                                           Sodium polyoxyethylene (3)                                                    tridecyl sulfate      11.6     8.0                                            Polymer JR 400, 2% aq. soln.                                                                        50.0     1.0                                            Water                 15.8       0                                                                  100.0    19.0                                                           neutralized to pH 6.7                                                         with HC1.                                                 ______________________________________                                    

This shampoo formula is a clear, syrupy liquid which foams very wellwhen used as a hair shampoo. After rinsing, the hair is left withexceptional wet-comb and untangling properties.

    ______________________________________                                        Product of Invention % by weight                                                                              % active                                      ______________________________________                                        B. Condensate of lauric acid and                                              aminoethylethanolamine reacted                                                with monoethylmaleate, unhydrolyzed.                                                               30.0       14.0                                          C. Condensate of lauric acid and                                              aminoethylethanolamine reacted                                                with monoethylmaleate, hydrolyzed.                                                                 31.6       14.0                                          D. Condensate of lauric acid and amino-                                       ethylethanolamine reacted with mono-                                          methylmaleate.       29.2       14.0                                          E. Condensate of lauric acid and amino-                                       ethy1ethanolamine reacted with mono-                                          methylmaleate, hydrolyzed.                                                                         29.6       14.0                                           Sodium polyoxyethylene                                                        (3.5) lauryl sulfate                                                                              20.0       5.0                                            Polymer JR-400       1.0       1.0                                            Water               q.s.         0                                                              All neutralized by pH 6-                                                      7 with either                                                                 NaOH or HC1.                                               Results:                                                                       B. Clear, syrupy liquid with good cream rinse action                         and conditioning properties when used as a hair shampoo.                       C. Very slightly hazy, syrupy liquid. Good wet-comb                          and untangling properties when used as a hair shampoo.                         D. Very slightly hazy, syrupy liquid. Very good cream                        rinse action and wet-comb properties when used as a hair                      shampoo.                                                                       E. Very slightly hazy, syrupy liquid. Very good wet-                         combing properties when used as a hair shampoo.                                                    % by wt.  % active                                       ______________________________________                                        Condensate of lauric acid and                                                 aminoethylethanolamine reacted                                                with monoisopropylmaleate.                                                                         26.8      12.7                                           Sodium polyoxyethylene                                                        (3.5) lauryl sulfate 18.2      4.6                                            Dimethylcocoamine     9.1      3.6                                            oxide                                                                         Polymer JR-400        0.9      0.9                                            Water                45.0        0                                                               neutralized to pH 6.7 with NaOH.                           ______________________________________                                    

This is a very slightly hazy, syrupy liquid, which foams well when usedas a hair shampoo.

I claim:
 1. A nitrogeneous compound of the formula ##STR22## wherein Ris an alkyl or alkenyl group of 5-25 carbon atoms; each R₁ is analkylene group of 2 to 4 carbon atoms and may be the same or different;nis 0 to 4; R₃ is alkylene of 1 to 4 carbon atoms y is 0 to 1; Z is + y;M is selected from the group consisting of hydrogen and a cation and Acis a saturated residue of an α,β-unsaturated dicarboxylic acid of 4 or 5carbon atoms wherein the carboxylic acid groups are on adjacent carbonatoms and the double bond is between two carbon atoms or immediatelyadjacent to one of them and wherein one of the carboxylic acid groupsmay be neutralized with a base or esterified with an alcohol of 1-6carbon atoms.
 2. A compound according to claim 1 wherein n is
 0. 3. Acompound according to claim 2 wherein y is
 0. 4. A compound according toclaim 3 wherein R is undecyl.
 5. A compound according to claim 4 whereinthe α,β-unsaturated acid is selected from the group consisting ofmaleic, fumaric and itaconic acids.
 6. A compound according to claim 5wherein the α,β-unsaturated acid is selected from the group consistingof maleic and fumaric acids.
 7. A compound according to claim 5 whereinthe α,β-unsaturated acid is itaconic.